Monocarboxylic acid esters of polymethylol phenols and process for preparing them



Pet -nuan e. '9, 1941 l -'2,-265,l4l 1 UNITED STATE METHYLOL PHENOLS AND PBDCESB PREPABING'THEM Herman A. 'Bruson,'- lhlladelphia;-ra., aislgnor to The Besinous Products & Chemical Compuny. Philadelphia, Pa.

No Drawing.

pplicatlon my 10. -1111a Serial No.2'i2,804 g 11 Claims. (0l. zoo-+179) This invention relates to esters of polymethylol phenols. It deals in particular with a method -'Zlhey include phenol, the threecresols,11,2,3- xylenol, the alkyl phenols having from 2 to'18- of preparing such esters and with the new compounds thus produced. 1

hydroxyl group. Such phenols are herein briefly referred to as "polymethylol-iorming phenolsq' I somuonand the mixture cooled to 20 C. The 7 carbon atoms or more in the alkyl group, cyclo alkyl phenols such as cyclohexyl or camphyl Methylol derivatives of phenols, such as are 5 phenols, aralkyl phenolssuch'as benzylphenols, obtainable by condensing formaldehyde and phey Phenols siwh phenyl phenol, n l l e nol orhomolo fles thereoi in alkaline solution, 7 phenols such -as p,-p'-dihydroxy diphenyl proas is well known, readily go over into resins when i D n p,p"-dihvdr xy 'di en Ysulfone, m heated. This is particularly true when they are dihydl xy d i h ny e hane, and polyh dric heated with acids, acid anhydrides, .or alkalies. 10 phenols suchas 'resorcin 1 51 8 py fl For example, saligenin (ortho-methylol phenol) echol. o hy n a' d'i substitution readily gives a resin when heated with acetic Products. v Y

anhydrlde. (Beilstein and Seelheim, 'Liebigs 4 he whlchgpossess ee avefla n e Annalen der Chemle 117, 87 (1861).) When two positions i e io with, r a de yde. 1 or more methylol groups are present in t p such as phenol itself .ormetacresol, are readily nolic nucleus, the tendency to form resins is converted i esters o the hitherto unknown greatly increased, so much so in fact, that mere- -;trimethyl0l p en l trim l 1y heating these compounds to l00-'110 C. give spectively. Phenols possessing iour available resins oi the insoluble or iniusible type. i nuclear positions orthoto the phenolic'hydroxyl One Object of the present invention is to pro-v 2 G p 3 example}, D P'- y r y phemll vide a method for preparing esters of polymeth-- D P ,'ale converted into dlmethylol or tetylol' phenols wherein both the phenolic hydroxyl lamethylol esliers-v This-is in part already d sgroups and the methylol groups are esterified. closed 111,8, imp d pp n. ial N0- Another object. is to make available esters, the 2 ,773, flled- March 14, 1 n w P nt N0- most important of which are included in the 1 4, issu d No m 5, 9 1 general formula 1 -'In the ester'ification procesaone mol of mono- PM. carboxylic acid anhydride is used for each aminomethylene group and for each phenolic I hydroxyl group which-is to be esterifled. Or the euro-A); 80 phenolic hydroxyl groups may be left-substanwherein R represent an aromatic h drocarbon 'uen! unesterifled. if desired, by using only radical of the hem ne series, A is theyacyl radk enough acid anhydride to react with the aminocalota monocarboxylic acid, n is an integer methylene W from ,1 to 3 inclusive, and a: is an integer from In'the Preferred-form of this mventmnit 2 t 4 inclusiva sun another object is to 3., been :found advantageous to esterify all the free duce esters of polymethylol phenols without sub- .mtential hydmxyl 011135 in the cmpunds stantial conversion of the reactants to resins, used and to employ t Purpese the In accordance with this invention any phenol drides of the lower aliphatic monobasic acids, p ble of forming a polymethylol derivative by Such as, for example, acetic, propionic,-or butyric. reaction with. tormaldehy'dais condensed with h It is tov be u however that at least two molecular equivalents each or formthe lanhydtrides higher aliphatic acids 9 aldehyde and a strongly basic, .nomammaflc, other carboxylic acids oi the aliphatic, aromatic,

, secondary amine such as dimethylamme to form alicyclic or heterocyclic series can be used, for. a. non-resinous nitrogenous condensation prod- ,mstance benzele enhydndeeremmc d uct, which is subsequently heated with reacting fume kanhydflde' hexmdmbewlc tproportionsoi' a monocarboxylic acid anhydride, l I 1.

- whereby the nitrogen group is split oil. and the The following examples illustrate this mven desired ester of the polymethylol phenol is obtained in non-resinous form. The pure esters 1 thus obtained are definite chemical compounds. Grams The, reaction is applicable to all phenols which Phemfl (1 mol) 94 passes at least two free reactive hydrogenatoms 25% dimethylamme solution (4 mols) 720 in the Nations ortho and para to the phenolic 30% formaldehyde solution (3.5 mols). 350

The phenol is dissolved in the diniethylamine hours. To

' theory.

formaldehyde solution is then added dropwise to the mixture while the mixture is stirred and cooled to 20-25 C. The addition requires about "30 minutes. The mixture is stirred for ten minutes lon'ger at20-25" C. and then is heated under reflux at 90- C. for about one and one-quarter e hot solution, 200 g. oi sodium chloride is added and the. hot mixture stirred for 20 minutes. The oil layer is separated from the hot solution and distilled under reduced pressure, the traction B. P. 130-150 C./1-2 mm. being collected. The yield is 228 g. of tri-(dimethvlamino-methyl) -phenol.

A mixture consisting of 132 g. of the above tri- -(dimethyl-amino-methyl) -phenol and 255 g. of acetic anhydride is boiled under reflux for 3 I hours and the'product distilled under reduced pressure. The fraction boiling between-175 and 210 -C./1 mm. is collected as the desired 2,4,6- trimethylol phenol tetra-acetate. It'is a colorless, viscous oil. 3 The yield is 154 g. Its formula omooocn cmococln HiOGOCHI When pure, it boils at zoo-21w c./1-2 mm. Upon catalytic hydrogenation with Raney nickel at 175C. anda hydrogen pressure of 1500-2000 lbs. per square men, it splits oflacetic acid by hydro-v genoiysis and gives the acetate oi 2,4,6-trimethylphenol, from which 2,4,6-trimethylphenol can be obtained by saponiflcation.

Example 2 e Grams Meta-cresol (1 mol) 108 25% dimethylamine solution (4 mols) 720 80% formaldehyde solution (3.5 mols) 350 The meta-cresol is mixed with the dimethylamine solution and the mixture cooled, treated with the formaldehyde, and worked up as in Example 1. The tri-(dimethylamino-methyl-m-cresol distills over at 138-145 C./2 mm. P

84 g. 0! the above tri-(dimethylamino methyl) m-cresol and 153 g.'-oi acetic anhydride is boiled for two and three-quarter hours under reflux,

and the product distilled under reduced pressure.

The iractionboiling between 185* and- 205 C./1 mm. is the desired 2,4,8-trimethylol-m-cresol tetra-acetate having theiormula omoooo moooom I moooo'm When pure, it is a colorless, viscous oil boiling at 195-200 C./0.5-'1 mm. The yield is 85% oi' Example. 3 o

To a solution consisting of 300 cc. of 404 cc. of 25% dimethylamine solution and .288 g. of p,n-dihydroxy diphenyl propane-2 there is gradually added 204 cc. of 30% formaldehyde while the mixture is stirred and cooled to 25-30 C. The reaction mixture is allowed to stand for 18 hours at ordinary temperature and then is heated at 60-65 C. for a half hour. The solvent,

water, and volatile materialis then removed by methanol,

heating the product at 100 C. under reduced pressure, leaving as a residue 842 g. of a brown, viscous oil containing 8% nitrogen by analysis. This substance consists essentially of dl-(dimethylamino-methyl)-p,p'-dihydrox y diphenyl propane-2.

A mixture or 34 g. oi this substance and 45 g.. acetic anhydride is boiled for three hours under reflux, and the product is distilled under reduced pressure. Dimethylol-p,p-dihydroxy diphenyl propane tetra-acetate distiils over between 240 a and 260 C./1 mm. as a colorless oil which. on

cooling. iorms a thick, balsam-like mass having a saponiflcation number 495, as compared to the calculated value 492. I

Example 4 Grams D.D'-dlhydroxy diphenyl propane-2 114 Methanol 100 dimethylamine solution 450 80% formaldehyde solution 225- The formaldehyde is added dropwise to the methanol solution 01' the dihydroxy diphenyl propane and dimethylamine solution while cooling to 20-30 C. Thereafter the mixture is boiled for one and one-quarter hours under reflux. The viscous oil layer is separated. washed with water, taken up in benzene, washed again with water, and dried in vacuo at C.at 25 mm. The dark, viscous mass obtained gradually crystallizes on standing to tetra-(dimethylamino-methyD- dihydroxy diphenyl propane-2, which, after re-.

'crystallization rrom petroleum ether, forms colorless crystals melting at 83 C. For conversion to the hexa-acetate, either the crystalline or the crude, viscous compound may be used.

91.2 g. of the crystalline product obtained above is boiled under reflux for three hours with 153 g. of acetic anhydride. The reaction product is heated in vacuo at 1 mm. at 100' C. to remove volatile materials. The residual product forms a pale amber-colored, viscous oil which cannot be .distilledat 1 mm. pressure without decomposition. Its acetyl value corresponds to the tetramethylol-p,p'-dihydroxy diphenyl hexa-acetate, havingthe probable formula The formaldehyde is added dropwise at 20-30 C. to the cooled mixture of the hydroquinone and dimethylamine. The mixture is stirred for three hours thereafter at room temperature, and the crystalline product filtered oil and recrystallized from alcohol. The yield is 90 g. of iii- (dimethylamino-methyD-hydroquinone, M. P. C.

45g. 0! the above product is boiled with 90g.

of acetic anhydride for three hours under reflux.

propane-2 ganic molding powders, films, 01' sheets on cooling, the mixture solidifies to crystals oi hydroquinone-2,5-dimethylol-tetra-acetate, having' the formula oooom CHIOCOICI CH3COOCH coon The yield is 43 g. The compound crystallizes from benzene in colorless crystals,M. P. 119 C.

- Example 6 A mixture consisting of 122 g. of acetic anhydride and 61.6 g. of di-(morpholino-methyhresorcinol is boiled under reflux for two and three-quarter hours. The reaction product is then distilled under reduced pressure. The fraction boiling at 193-197? C./1 mm. is the desired dimethylol resorcinol tetra-acetate. The di- (morpholino-methyl)-resorcinol used above is obtainable by-condensing resorcinol with 2 mols each of iormaldehyle and morpholine, as described in applicant's U. S. Patent No. 2,040,040.

Example 7 .A mixture consisting of 65 g. of di-(morpholino-methyD-pyrogallol and 153 g. of acetic anhydride is boiled for three hours under reflux. Upon distillation of the reaction product in vacuo, the desired penta-acetate of dimethylol pyrogallol distills over at 235-245 C./l-3 mm. as a colorless, viscous mass, which solidifies when cold. After recrystallization from alcohol, it

, forms colorless crystals which melt at 75-76 C.

.The di-(morpholino-methyll-pyrogallol used above is obtainable by condensing pyrogallol with 2 mol equivalents each of formaldehyde and morpholine, as described in applicants U. S. Patent No. 2,040,040.

In the above examples, the acetic 'anhydride can be replaced byv a molecularly equivalent quantity of propionic. anhydride, butyric anhydride, crotonic anhydride, or the anhydride of any other monocarboxylic acid, to yield analogous esters of polymethylol phenols.

' Finally, the dimethylamine or morpholine used in the above examples can be replaced by other non-aromatic, secondary amines, such as diethyldicyclohexylamine, and the like.

The products are useful as plasticizers for orand as intermediates for making resins.

I claim: 1. A process for preparinga non-polymeric ester of a polymethylol phenol and a monocarboxylic acid, which comprises condensing reacting proportionsof a monocarboxylic acid anhydride with a nitrogenous condensation product of a phenol having at least'two of the nuclear hydrogen atoms ortho and para to the hydroxyl group available for reaction and at least two molecular equivalents each of formaldehyde an a non-aromatic, secondary amine. Y

. amine, piperidine, pyrrolidine, diethanolamine,

portion of the non-resinous nitrogenous condensation product obtained by condensing one molar proportion of a phenol having at least two of the nuclear hydrogen atoms ortho and para to the hydroxyl group available for reaction with at least two molar proportions each of formaldehyde and a non-aromatic,.secondary amine.

4. The processof claim 3 in which the acid anhydride is acetic anhydride.

5. A method for preparing an ester of a polymethylol phenol, which comprises condensing a phenol having at least two of the nuclear-hydrogen atoms ortho and para to the hydroxyl 'group available for reaction with at least two molecular equivalents each of formaldehyde and of 'a non-aromatic, secondary amine, separating the condensation product thus formed, and reacting saidcondensation product with a monocarboxylic acid anhydride.

6. As a new chemical compound, an ester of a 2,4,6-trimethylol phenol and a lower fatty acid.

7. As a new chemical compound, 2,4,6-trimethylol phenol tetra-acetate.

8. As a new chemical compound, 2,4,6-trimethylol-m-cresol tetra-acetate.

9. As a new chemical compound, tetramethylol- D,p-dihydroxy diphenyl propane-2-hexa-acetatehaving the formula ococm' c1130 OOCHrcmococm CHr- 0H'.

omcoocn cmocoon.

10. As a new chemical compound, a non-polymeric ester of a polymethylol phenol in which the hydrogen atoms of the phenolic and of the 00 methylol groups are replaced by the acyl radical of a monocarboxylic acid.

2. A process for preparing an ester of a polymethylol phenol and a monocarboxylic acid 11. As a new chemical, compound, a non-polyfneric ester of a trimethylol phenol in which the hydrogen atoms of the phenolic and of the. 35 methylol groups are replaced by the acyl radical of a monocarboxylic acid.

A. BRUSON.

which comprises condensing at least two molar- I proportions of a monocarboxylic acid anhydride 

